Certain trichloromethyl-substituted oxadiazoles and oxadiazolinones



United States Patent Ofiice 3,326,931 Patented June 20, 1967 3,326,931 CERTAIN TRICHLOROMETHYL-SUBSTITUTED OXADIAZOLES AND OXADIAZOLINONES Venkatachala L. Narayanan, Highland Park, and Jack Bernstein, New Brunswick, N.J., assignors to Olin Mathieson Chemical Corporation, New York, N.Y., a

corporation of Virginia No Drawing. Filed Aug. 12, 1965, Ser. No. 479,282

9 Claims. (Cl. 260307) This invention relates to new oxidiazoles and oxadiazolinones. These new compounds can be represented by the formulae wherein n is a positive integer less than eleven, and R is cyano, carboxy or carbalkoxy [preferably carbo (lower alkoxy)], the preferred compounds being those wherein n is two or three.

These new compounds are useful as soil fungicides, in that when mixed into the soil at a concentration of about 50 ppm. they protect seeds and plants against a broad spectrum of pathogenic fungi, like species of the fungal genera Pythium, Fusarium, Rhizoctonia and Sclerotium. Moreover, since they are less volatile than the corresponding thio derivatives (i.e., the thiadiazoles and thiadiazolinones) they retain their antifungal activity after being mixed with soil longer than do said thio derivatives.

The compounds of this invention are prepared in mixture by a two-step process of this invention. In the first step, O-ethoxycarbonyltrichloroacetamidoxirne is heated to yield 3-trichloromethyl-A -1,2,4-oxadiazolin-5-one, a new intermediate of this invention. The resulting 3-trichloromethyl-A -1,2,4-oxadiazolin-5-one is then treated with a compound of the formula wherein n and R are as hereinbefore defined and X is bromo or preferably iodo to yield a mixture of the final products; the reaction preferably being carried out in the presence of silver oxide. The resulting mixture can then be separated by vapor phase chromatography.

The following examples illustrate the invention (all temperatures being in centigrade).

EXAMPLE 1 5-etlz0xy-3-trichloromethyl-I,2,4-0xadiaz0le and 4-ethyl- 3 -trich lorometh yl-A -1 ,2,4-xadiaz0lin-5-0n-e Preparation of 3-trichloromethyl-A -1,2,4-0xadiazolin- 5-one.A solution of 72.3 g. of trichloroacetonitrile in 100 ml. of anhydrous ether is added dropwise with stirring at a temperature of 510 to a suspension of 16.5 g. of hydroxylamine in 1.5 l. of anhydrous ether (addition time 1.5 hour). Stirring at 510 is continued for an additional hour. The mixture is then transferred to a separatory funnel and washed with 25 ml. of ice cold water. The clear ethereal solution is dried over anhydrous MgSO Evaporation of the ether gives 67.5 g. of a yellowish white solid, M.P. 115-119". It is crystallized from a 1:1 mixture of benzene and hexane to give 52.5 g.

(59%) of 2,2,2 -trichloroacetamidoxime as shiny white crystals, M.P. 125.

A stirred mixture of 8.9 g. of 2,2,2-trichloroacetamidoxime and 7.5 ml. of ethylchloroformate is placed in an oil bath and its temperature raised slowly during 30 minutes to At 75, the reaction mixture (half solid, half liquid) is removed from the oil bath and stirred for 15 minutes. The exothermic reaction (temperature rising to subsides during this time. The mixture is again heated to 8090 for an additional 15 minutes, and subsequently allowed to cool. The addition of 30 ml. of dry ether results in the precipitation of trichloroacetamidoxime hydrochloride which is filtered off and washed with anhydrous ether. The ether solutions are combined, washed with water (30 ml.) and dried over MgSO Slow evaporation of ether gives 5.2 g. (43%) of white crystals, M.P. -102". These crystals are O-ethoxycarbonyltrichloroacetamidoxime.

24.95 g. of O-ethoxycarbonyltrichloroacetamidoxime is pyrolyzed at (pre-heated oil bath) for 45 minutes. On cooling, a yellow thick oil is obtained which solidifies on the addition of hexane and scratching, 19.2 g., M.P. 103125. Two crystallizations from a mixture of chloroform and hexane gives about 8.5 g. (41%) of white crystals of 3-trichloromethyl-A -1,2,4-oxadiazolin-5-one, M.P. about 129 131.

Analysis.Calcd. for C HO N C1 C, 17.71; H, 0.50;

N, 13.76; Cl, 52.27. Found: C, 18.18; H, 0.82; N, 13.25;

EXAMPLE 2 (a) Preparation of fl-iodopropionitrila-A solution of 32.0 g. of freshly distilled fi-bromopropionitrile (64- 66/5 mm.) and 66.0 g. of sodium iodide in 400 ml. of dry acetone is stirred at room temperature for 20 hours. Evaporation of the solvent and washing with sodium thiosulfate solution gives an oil which when fractionally distilled yields 40.6 g. of ,B-iodopropionitrile, B.P. 101- 103 /23-25 mm.

(b) Preparation of a mixture of 5-(2-cyan0eth0xy)-3- zrichloromethyl-I,2,4-0xadiaz0le and 4-(2-cyan0ethyl)-3 trichloromethyl-A -l,2,4-0xadiaz0lin 5 one.T0 a mixture of 20.3 g. of 3trichloromethyl-A -1,2,4-oxadiazolin- 5-one and 23 g. of silver oxide, 17.4 g. of 8-iodopropionitrile is added slowly with strong cooling. The mixture is then heated to 7075 with stirring for 2 hours. The solid is filtered off and the unreacted fi-iodopropionitrile is removed in vacuo giving an isomeric mixture of 5-(2- cyanoethoxy)-3-trichloromethyl-1,2,4-oxadiazole and 4- g2-cyanoethyl)-3-trichloromethyl A -1,2,4-oxadiazoline- -one.

(o) Separati0n.By preparative gas chromatography on K-22A Column, the above mixture obtained in step (b) is separated into its pure components.

EXAMPLE 3 5 2-carb0xyethoxy) -3-trichl0r0methyl-I,2,4-0vcadimz0le To 12.5 g. of 5-( 2-cyanoethoxy)-3-trichloromethyl- 1,2,4-oxadiazole, 60 ml. of concentrated hydrochloric acid is added cautiously with stirring. The mixture is heated at 70-80 for 6 hours. Water is added after cooling, and the mixture is extracted with ether. The ether solution is extracted repeatedly with 10% sodium carbonate solution. The combined sodium carbonate extracts are acidified and extracted with ether. The ether solution is evaporated leaving 5-(2 car boxyethoxy) 3 trichloromethyl- 1,2,4-oxadiazole. It may be crystallized from benzenepetroleum ether.

3 EXAMPLE 4 5 -(2-carbethoxyethoxy -3-trichlor0methyl-1 ,2,4- oxadiazole A mixture of 25.6 g. of S-(Z-cyanoethoxy)-3-trichloromethyl-1,2,4-oxadiazole, 75 ml. of 95% alcohol and 3 cc. of water is poured into a citrate bottle and saturated with hydrogen chloride at O5. After 12 hours at room temperature, the mixture is heated for 2 hours on the steam bath, cooled, 50 ml. of water added, the oily layer separated, and added to the ether extract of the aqueous layer. The ethereal solution is dried over anhydrous magnesium sulfate. T he solvent is removed and the oily liquid distilled in vacuo to yield 5-(2 carbethoxyethoxy) 3 -trich1oromethyl-1,2,4-oxadi-azole.

EXAMPLE 6 4-(2-carbeth0xyethyl) -3-trichl0r0methyl-A -1,2,4- oxadiazolin-S-one whenin n is a positive integer less than eleven, and R is selected from the group consisting of cyano, carboxy, and carbo(lower alkoxy).

2. 5-(2-cyanoethoxy)-3-trichloromethyl 1,2,4 oxadiazole.

3. 5-(2-carboxyethoxy)-3-trichloromethyl-l,2,4 oxadiazole.

4. 5-[2-carb0(lower alkoxy)ethoxy]-3-trichloromethy1- 1,2,4-oxadiazole.

5. A compound of the formula wherein n is a positive integer less than eleven, and R is selected from the group consisting of cyano, carboxy, and carbo(lower alkoxy).

6. 4-(2-cyanoethyl) 3 trichloromethyl A 1,2,4- oxadiazolin-5one.

7. 4-(2-carb0xyethyl) 3 trichloromethyl A 1,2,4- oxidazolin-S-one.

8. 4-[2-carbo(lower alkoxy)ethyl]-3 trichloromethyl- A -1,2,4-oxadiazolin-5-one.

9. 3-trichloromethyl-A -1,2,4-oxadiazolin-S-one.

References Cited UNITED STATES PATENTS OTHER REFERENCES DAlo et al., Chem. Abstracts, vol. (1964), col.

M-oussebois et 211., Helv. Chim. Acta, vol. 47 (1964), pp. 838-48.

Wiley, Heterocyclic Compounds, Interscience, 1962, p. 25-6.

ALEX MAZEL, Primary Examiner. RICHARD J. GALLAGHER, Assistant Examiner. 

1. A COMPOUND OF THE FORMULA
 5. A COMPOUND OF THE FORMULA 